Process of alkylating phenols



Patented Dec. 2, 1941,

- OFF CE Mortimer '1. Harvey, East'Orange, N. J., assignor, .by mcsne assignments, to Hand Research Corporation, a corporation of New Jersey No Drawing. Application February 11, 19st, Serial No. 190,037 I a 11 Claims.

The present application is a continuationin part of my copending application Serial Number- 23,022,'flledMay 23, 1935, issued March 21, 1939, Patent No. 2,150,920.

I have discoveredthat certain tertiary alkyl alcohols and certain phenols can be condensed to form the ethers thereof and the corresponding alkyl substituted phenols; with more than about one-quarter and less than one-half mole of sulphuric acid per mole of phenol as the condens- Two-tenths of a mole and eighting agent. jtenths of a mole of concentrated sulphuric acid per moleof the phenol used can be stated to be practical lower and upper limits, respectively, of the amount oi. sulphuric ,acid used. Withlless than the lower limit-the reaction is slow and.

more than about the upper limit at the higher concentrations is not necessary because of the speed-oi' the reaction therewith. Under'some conditions of temperature and concentration thesulphuric acid is added gradually, under other conditions the sulphuric acid can be added all at once, and illustrative examples of the practice of the present invention givenv below will show various ways of adding thesulphuric acid.

lower concentrations; from about sixty-five per cent to about eighty-five percent for examples,

' .the sulphuric acid'can be addedat temperatures speed of reaction desired and uponthe desiredpurity of the reaction products; for the higher concentrations the sulphuric acid can be added.

advantageously at lower temperatures, for example, from about C. toabout C. In some the reaction solution, after the addition of the sulphuric acid, can be-warmed up or heated to speed the reaction. And these examples are given merely-as general illustrationsoi thepractice of the invention and not, as limitations thereon. The inventionrelates generally to the alkylation of phenols with tertiary alcohol, using between about one-quarter and about one-half mole of sulphuric acid as the condensing agent, the reaction product being tertiary alkyl ethers of phenols, or tertiary alkyl substituted phenols or mixtures thereof. By this method a high yield is easily obtainable, for example, from about 90% to 100%, without sulphonation and without the formation of any substantial amount of byproducts.

Theconditi n is more advantageous for the reaction whe there is a minimum amount ofwater in the reaction mixture so that the best condition theoreticallyis when the tertiary a1- cohol, the phenol and the sulphuric "acid are substan'tiallyjree of water, but commercial grades 'are suitable vfrom a manufacturing standpoint, that iswhen there is present about thirty per cent or less water" with respect to the total of sulphuric acid and water. Illustrative examples of suitable and commercially available concentrationsof reagents and sulphuric acid are ter- .tiary butyl alcohol, substantially 94% and substantially 100% phenol (carbolic acid) 92% and 15 100%; and sulphuric-acid, 96%, 94% and fuming,

In some cases, the total amount of water can be as high as calculated on total sulphuric acid and water, considered from. the standpoint of practical manufacture and cost on a commercial scale.- a v Although the melting point of one of theme- .terials to be reacted, tertiary alcohol or phenol,

- may behigher than the temperature at which the sulphuric acid is added, as solidiiyirfg point of the tertiary alcohol-phenol solution is considerably below the melting point 'of either of these ingredients and below the temperature at which the sulphuric acid is generally added, so that the method of the presentinvention has the even the lower temperatures when desired. I According to' the present invention, particularly the stepsindicated above, a substantially theoretical yield of tertiary alkylated phenol isoproduced andthe yield comprises a tertiary alkyl ether of the phenol or the corresponding tertiary alkyl substitutedphenol or mixtures thereof, and this method is operative with the various phenols, including phenol (carbolic acid) the three cresols and :the four xylenols, the proportion of alkyl-' phenol ethers to substituted phenols in. the yield varyingwith the particular phenol used. Illustrative examples of the tertiary alkyl alcohols'suitable for the practice of the present invention are tertiary butyl alcohol, tertiary amyl alcohol, and-the various ones 01' the tertia hexyl alcohols, thfltertiary heptyl alcohols, th tertiaryoctyl alcohols, and so on. v

Now, when the fraction of a mole of concentrated sulphuric acid is added to obtain the substantially completely tertiary alkylated phenol, namely the tertiary alkyl etheroi the phenol or" the tertiary alkyl substituted phenol or mixtures thereof, a milkiness occurs in the solution'when c water 01? reaction reaches a certain concentraadvantage of working with liquid solutions at v tion and comes out of .solution, and after this the water of reaction separates in a distinct layer from the reaction products. And this milkiness can be obtained directly by adding sulphuric acid at predetermined concentration and temperature or can be obtained by leaving the solution of tertiary alkyl alcohol, phenol and concentrated sulphuric acid to stand until the reaction takes place, for example, for several hours or for over night. 7

Further as to the temperature at which the sulphuric acid is added, it is noted that it is added at such a rate and at such a temperature that no substantial amount of sulphonation or other undesirable reaction takes place and the temperature and rate at which the sulphuric acid is added are governed to suit the degree of purity desired in the final product.

In the latter case, that is when said solution is left to stand, as for several hours or over night,

- about one-quarter moleto about one-half mole of concentrated sulphuric acid added gradually at lower temperatures will give complete alkylation to a mixture of tertiary alkyl ether of the phenol and tertiary alkyl substituted phenol, and to obtain milkiness in the solution. As examples'ot added gradually to said solution at about C..

to about 25 C. This is substantially 0.3 mole of the sulphuric acid per mole of phenol. The reaction material were leit to stand at room temperature. and the milky condition appeared sudcomparative times of reaction to the milky state when using less than one-half mole of sulphuric acid it is noted that when about three-tenths (0.3) of a mole of sulphuric acid is added gradually at about 15 C. to a reaction mixture or solution of tertiary butyl alcohol and phenol (carbolic acid) it takes about ten Hours or more for the milkiness to appear, so generally the concentrated sulphuric acid can be added to the reaction solution in the late afternoon and left to stand overnight; and when four-tenths (0.4) of a mole of sulphuric acid is added-gradually at about 15 denly at the end otabout ten hours. The reaction product is for the most part tertiary butyl ether of phenol with some tertiary butyl phenol, and the yield is close to the theoretical, that is about 100%.

Example 2. --With about 940 grams of 100% phenol and 740 grams of 100% tertiary butyl alcohol and 400 grams of 94% H2804, under conditions similar to those of Example 1, the milky condition appeared after thirty minutes standing.

' In this case the amount of sulphuric acid used was about0.4 mole per mole oi phenol. Substantially the same high yield was obtained but with a slightly higher percentage 01' tertiary alkyl substituted phenol. a p

' Example 3.-With about 940 grams of 100% phenol,"140 grams of 100% tertiary butyl alcohol and 500 grams of 94% H1804, under conditions similar to those of Examples 1 and 2, the milky condition. appeared immediately after the sul- C. the milkiness appears in about four hoursj.

However, a diflerencein temperature willcause the appearance of the milkiness to be'hastened or delayed. In the several comparative examples above given, the strength of reagents and sulphuric acid are the same, that is the percentage of-water in each of the reagents and the sulphuric acid is thesame for each of said materials,

the strengths, given as illustrations, being tertiary alkyl alcohol, about 100%; phenol (carbolic acid) about 92%; and sulphuric acid, C. P. at least 94%. Variations in the amount of. water affect the length of time required to reach the milky state and the time required for complete milkiness, other factors being constant. Also, just prior to or during the appearance of the milkiness heat is generated within the reagent materials or intermediate reaction products or mixture thereof, as the case may be, but'the consequent rise in temperature generally is' not such as will cause sulphonation or result in other undesired reactions, and the reaction mixture can be left to stand at room temperature or at. elevated temperature, as the case may'be, without artificial cooling oz-heating.

The products obtained by condensing tertiary alkyl alcohols with phenols by using between about one-quarter and about one-half mole of concentrated sulphuric acid as the condensing agent, namely, a tertiary ,alkyl ether of phenol or the corresponding tertiary alkyl substituted phenol or a mixture thereof, is suitable, .Ior example. for condensation with an aldehyde, e. g., formaldehyde, to obtain resinous materials,in which case both the said etherand substituted phenol react with the aldehyde to form the resinous product. And the products of the present invention are suitable-for general use.

substantially 0.4 mole oi sulphuric acid per phuric acid had all been added. This i about 0.5 mole of the sulphuric acidper mole of phenol. Here also the high yield was obtained, with ,a still higher proportion of substituted phenol.

Example 4. witn about grams of 92% phenol, 74 grams of 100% tertiary butyl alcohol and 40 grams of 94% sulphuric acid, under conditions similar to those of Examples 1, 2 and 3, the milky condition appeared in about four hours. Thisis about 0.4 mole of sulphuric acid per mole of phenol and comparison can be taken between this example and Example 2 which also used 0.4

mole sulphuric acid-per mole of phenol. The dib.

ference between; these two examplesuis, the

strengthiwater eontentlfoi! thephenplia dthe consequent eii'ective dilution of the sulphuric acid, and the resulting extension of time required for milkiness, from about thirtyminutes in Example 2 to about four hours in the presentexample.

Example 5.-With about .940 grams of 100% phenol, 74 grams oi 100% tertiary butyl alcohol and about 570 grams of 70% sulphuric acid, it took 48 hours for'milkiness to appear This is mole of phenol.

Example 6.To a solution of about 282 grams of 100% phenol and 222. s of .tertiary butyl alcohol which is at about 40? C. are added a solution of 45 grams of water .in grams oi' over 94% sulphuric acid, the sulphuric acid solution being'at about 16 C. This is abopt seventy per cent sulphuric acid and the amount of sulphuric acid is about 0.4 mole with respect to the reagent materials. The sulphuric acid solution was added all at once to the reagent solution. In about ten hours milkiness appeared, and substantially one hundred per cent of mixture of tertiary butyl ether of phenol and tertiary butyl phenol was produced.

Example Zr-Molecular proportions of 1,4-dimethyl-Z-hydroxy-benzene and tertiary butyl alkyl ether of a phenol, or tertiary alkyl substituted phenol, or mixture of these two'latter, can be washed to free it of any excess of the sulphuric acid left therein, but enough of the sulphuric acid can be left in to act as a catalyst for the condensation of the said products of said exampies with an aldehyde, such as formaldehyde,

was left to stand at room temperature and in about four hours the milkiness of the discharged sulphuric acid and water appeared. The reac tion was substantially complete and gave a substantially theoretical yield of a mixture of the tertiaryl butyl ether ofthe l,4 -dimethyl2-hydroxy-benzene and the tertiary butyl substituted 1,4-dimethyl 2-hydroxy-benzene. The 1,4-dimethyl-2-hydroxy-benzene used in this example was a commercial grade containing over 90% 1,4- dimethyl-2-hydroxy-benzene with the balance other xylenols.

Example 8.-Molecular proportions of substantially 100% pure tertiary amyl alcohol and phenol (carbolic acid) are dissolved together and into the solution is added gradually four-tenths of a mole of concentrated sulphuric acid (over 94%) at about C. to C. after which the solution was left stand at room temperature. In about one and one-half hours the solution suddenly heated up and became milky, and a sulphuric acid-wafer emulsion settled down in a layer beneath the condensation products of the tertiary amyl alcohol and phenol. The yield'was I phuric acid the solution became milky but it took over twenty-four hours to become m yield was somewhat less than 100%.

With eight-tenths of a moi of concentrated sulphuric acid per mole of .phenol'the solution became-milky immediately after the sulphuric acid had all been added. I

The products of reaction of each of the above particular Examples 1 to 9, inclusive, "as well as ky and the of the other examples, both'the general and the more particular, are suitable, for reaction with. compounds containing reactive methylene groups such as formaldehyde, hexamethyiene tetramine, paraform, paraldehyde, furfuraldehyde, and the other well known aldehydic compounds, for making resins. These resin formingreactions can be carried on without or witha catalyst either acid or basic, in mannerwell known in the art of condensing phenois'and formaldehyde. The

ethers of the products of the present-invention will react at the same time as any of the substituted phenols present therewith to form resins with the aldehydic compounds. When acid catalyst is used, a partof'the acid used as the condensing agent for the phenol-tertiary alkyl alcohol condensation can be utilized. For example, in carrying on with the products of, any of the. examples above given for the purpose of making resins, the reaction product, tertiary al- 7 ally adding sulphuric acid to the"mixture,-.said

with the aid of heat.

Subject matter disclosed but not claimed herein is claimed in my copending applicationSerial Number 256,929, flied February. 17, 1939.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. The method of condensing aliphatic tertiary alcohols and'phenols which comprises mixing a phenol of thebenzene series and a tertiary alkyl alcohol in substantially equimolecular amounts,

and gradually adding thereto concentrated s'ulphuric acid in amount between about two-tenths and about eight-tenths of a molecular amount, and allowing the resulting solution to stand until a milkiness occurs.

2. The method of condensing aliphatic tertiary alcohols and phenols which comprises mixing a phenol of the benzene series and a tertiary alkyl alcoholin substantially equimolecular amounts, and gradually adding thereto concentrated sulphuric acid in amount between about two-tenths and about eight-tenths of a molecular-amount, allowing the resulting solution to stand until a milkiness occurs, and separating the water of reaction. I

3. The method of condensing aliphatic tertiary alcohols and phenols which comprises mixing a phenol of the benzene series and a tertiary alkyl alcohol in substantially equimolecular amounts, and gradually adding thereto concentrated sulphuric acid in amount between about two-tenths and about eight-tenths of a molecular amount, at a temperature below the boiling point of the tertiary alkyl alcohol used and allowing the re sulting solution to stand until a milkiness occurs.

4. The method which comprises mixing phenol and tertiary butyl alcohol in substantially equimolecular amounts, and gradually adding thereto concentrated sulphuric acid in amount between about two-tenths and about eight-tenths of a molecular amount, at a temperature below the boiling point of the tertiary butyl alcohol and allowing the resulting solution to stand until a milkiness occurs. c

5.. The method which comprises mixing substantially equimolecular proportions of phenolic -material'selected from the group consisting of phenol (carbolic acid), the cresols and the xylenols and a tertiary alkyl alcohol having from 4 four to nine carbon atoms, and gradually adding thereto concentratedsulphuric acid in amount between about two-tenths and. eight-tenths of a molecular amount by weight.

material selected from the roup consisting of phenol (carbolic acid), th cresols and the xylenols and a tertiary alkyl alcohol having from 'i'our to nine carbon atoms, and adding concentrated sulphuric acid in amount between about. 5 two-tenths and about five-tenths of a molecular amount by weight. 7. The method of condensing tertiary alcohols v and phenols which comprises mixing a phenol of the benzene series and a-tertiary alkyl alcohol in substantially 'equimolecular amounts, and gradu- 6. The method whichcomprises mixing substantially equimolecular-.proportions of. phenolic -cobol and the selected phenol in substantially equimolecular amounts as starting materials, and gradually adding concentrated sulphuric acid to said mixture, the sulphuric acid. being used in quantityibetween about two-tenths and eighttcnths'of a molecular equivalent of one of said startingmaterials, and holding said sulphuric acid in said solution until it comes out of solution with water formed by the condensation of said starting materials.

' -l1 The method'which comprlsesiorming an equimole cular mixture or a phenol 01 the benzene in a concentration of between sixty-five per cent and one hundred per cent and in a quantity of between about two-tenths of a mole and about eight-tenths of a mole per mole of phenol used and suflicient to remove the water produced by the condensation reaction of said starting materials.

9. The method which comprises mixing sub-- stantially equimolecular proportions of a phenol of the benzene series and a tertiary alkyl alcohol as starting materials and dissolving concentrated sulphuric acid in said mixture, the sulphuric acid being used in a quantity between about two-- tenths and eight-tenths of a molecular equivalent of one of said starting materials.

series and a tertiary alkyl alcohol and adding sulphuric acid thereto, the amount oi said sulphuric acid by weight used being between about two-tenths and about eight-tenths o! a-molecular equivalent or said phenol, the-strengthof said sulphuric acid with respect to total sulphuric acid and water in said solution being'between sixty-five per cent and one hundred per cent, the temperature at which the said sulphuric acid is added to said solution being between 0 C. and the boiling point of said solution,--and holding said solution with said sulphuric acid dissolved therein 10. The method of condensing a tertiary alkyl alcohol and a phenol of the benzene series, which comprises forming a mixture of the selected-ah 30 at a temperature between 0 C, and the boiling pointof said solution until. saidsulpliuric acid comes out of solution-with water formed by the condensation of said reagents.

' 4 Moa'mmaT; 

